KR790001093B1 - Asymmetric thioindigoid compounds for use in colouring organic polymeric materials - Google Patents

Abstract

Org. polymeric materials were coloured with asym. thioindigoid compds,(I; R = hydrogen atom or low grade alkyl radical, R' = hydrogen atom, low grade alkyl radical or halogen atom, R"= hydrogen atom or methyl radical, X=oxygen atom or sulfur atom) having good affinity to polyester fibers. polyester fibers dyed with I gave a clear color. Other org. polymeric materials such as PVC, melamine, polymetaacryl, polyamide, etc. could also be coloured with I

Description

Coloring of organic materials using novel asymmetric thioindigo-based compounds

The present invention is general formula (I)

Wherein R represents a hydrogen atom or a lower alkyl group, R 'represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a halogen atom, R "represents a hydrogen atom or a methyl group and X represents an oxygen atom or sulfur A novel asymmetric thioindigoid-based compound represented by (a) represents an atom.) Relates to a method for coloring an organic polymer material.

Thioindigoide compounds have long been known as vat color dyeing, most of which have been used to dye cellulose fibers, but have no affinity for polyester fibers, The dyeing effect of the dyeing method was almost impossible to recognize the dyeing effect, making it practically useless.

By the way, little is known about the asymmetrical thioindigooid compound represented by General formula (I). We synthesized various asymmetric thioindigoide-based alloys represented by the general formula (I), and examined the dyeing properties in various ways, and as a result, these compounds were compared with the corresponding symmetric thioindigoide-based compounds, Generally, the melting point is lowered, the solubility in the solvent is increased, the molecular absorption coefficient is increased, and the affinity for the polyester fibers is markedly increased.

Such a fact is a remarkable finding in view of the fact that a thioindigoide-based compound, which has been practically of little value as a dispersion dye for polyester, has been newly found to be useful as a dispersion dye for polyester.

It was unpredictable that the asymmetric thioindigoide compound exhibits such dyeing properties, and the significance of the present invention is particularly emphasized in this respect.

That is, the asymmetric thioindigooid compound of the general formula (1) used in the present invention exhibits good affinity for polyester fibers, and is dyed just like a general dispersion dye for polyester, for example, by applying a high-temperature dyeing method of 130 ° C. It can give an effect.

In addition to the features described above, the asymmetric thioindigooid compounds of the general formula (1) impart a vivid color from red color to crimson, and they have high light and hardness resistance. Since it is a sex, the industrial value for the method of the present invention should also be highly appreciated.

Moreover, since the compound of General formula (1) shows the favorable sublimation firmness in polyester fiber, it is pointed out that it is suitable for printing with the clearness of the color.

The novel asymmetrical thioindigoide compound of general formula (I) used in the present invention is a phenoxyphenylthioglycolic acid derivative represented by general formula (II) by the following route, or thiophenoxyphenylthioglycol. Known from phenoxythionaphthenonone- (3) derivatives or thiophenoxythionaphthenonone- (3) derivatives represented by the general formula (III) obtained by the Friedelcrafts cyclization method of an acid derivative. It can be manufactured easily by the method described above (in formulas (II) and (III), R, R 'and X mean the same as R, R' and X in formula (I), respectively). For example, the melting points of 6-phenoxythioindigo and 6-thiophenoxythioindigo obtained by this route were 240-242 ° C and 225-227 ° C, respectively.

As the organic polymer material to be the object of the present invention, polyester is particularly important, but various synthetic resins such as polyvinyl chloride, polyvinylidene chloride, polyolefin, polymethacrylic, polyester, and polyamide And melamine or urea formalin resins.

Table 1 shows an example of a novel asymmetric thioindigooid compound of general formula (I) used in the present invention.

TABLE 1

The coloring of the organic polymer material by the method of the present invention can be facilitated according to a method usually carried out using an asymmetric thioindigooid compound of the general formula (I). That is, when the organic polymer material is a fiber material, a general dust reduction method or a printing method in an aqueous medium can be applied, and a so-called thermosol process can be applied depending on the material.

In this case, the treatment temperature in the case of the dust removal method is preferably 80-140 ° C. In addition to the steaming process by saturated steam at 100-130 ° C for fixing the printing material in the printing method, 150 A steaming treatment with superheated steam at −180 ° C. may also be applied.

The application of the thermosol method is advantageous when the organic polymer material is a polyester fabric, and the dry heat treatment is preferably performed at 180-220 ° C.

In addition, when the organic polymer material is a general molding method, the compound of general formula (I) may be added and colored during the synthesis or molding process of the polymer material.

In addition, a fluorescent pigment and a base of a resinous color ranging from orange to red may be obtained by using the asymmetric thioindigooid compound of general formula (I).

The details of the invention will be explained in the following examples. "Part" in description shows a weight part.

Example 1

1 part of 6-phenoxythioindigo (Table 1, Compound 1) is mixed with 0.5 parts of an alkylbenzene sulfonic acid type or polyoxyethylene alkylaryl ether type surfactant and 2 parts of water, pulverized, and distilled with water to make a total of 10 parts Make an atomized dispersion.

0.2 part of this dispersion liquid is added to 500 parts of water baths containing 1 part of higher alcohol ester sulfate type surfactant, and it is made into a salt bath.

) 직물 10부를 넣고 130℃에서 40분간 처리, 수세 후 건조시킨다.Polyester processed yarn in this dye bath

) 10 parts of the fabric is added and treated at 130 ° C. for 40 minutes, and washed with water and dried.

The obtained saline showed a clear reddish fluorescence, and exhibited a light intensity (JIS L 0842-1971) grade 5 and a sublimation hardness (JIS L 0879-1968: No. B) grades 3-4.

Example 2

Using 6- (P-crophenoxy) thioindigo (Table 1,-compound No. 2), the atomization dispersion liquid was prepared like Example 1, 1 part of polyoxyethylene alkyl ether type surfactants 0.04 Dispersion is carried out in 20 parts of water containing parts to obtain a treatment bath. The polyester cloth is immersed in this treatment bath and impregnated with a high rate of 40-50%.

After drying the treated fabric and drying for 1 minute at 180 ℃, washed with diluted aqueous surfactant solution, washed with water again and dried.

The obtained application | coating showed clear fluorescent redish color, and showed the lightness intensity degree 5 grade and the sublimation hardness degree 3-4 grade.

Example 3

Using 6-phenoxythio indigo (the same as in Example 1), an atomized dispersion was prepared in the same manner as in Example 1, and then a polyester woven fabric was prepared.

Stock emulsion half emulsion

1 part of Neugen ET (surfactant manufactured by 1st Pharmaceutical Co., Ltd.)

14 water

Miner terpenor 35

50 parts sodium alginate (5%)

Colorful

Three parts of the dye paste of Example 1

36 parts of water

60 parts of stock paste

Reducing Agent Part 1

It printed on the pattern using the printing paste adjusted to the.

The printed woven fabric was subjected to thermal treatment for 3-5 minutes in HT Steamer at 150-180 ° C., then washed with diluted aqueous surfactant solution and washed with water again and dried.

The edge portion of the obtained woven fabric exhibited a vivid fluorescent red color, and exhibited a light resistance level of 5 and a sublimation hardness of 3-4.

Example 4

A homogeneous mixture consisting of 0.1 part of 6- (P-methylphenoxy) thioindigo (Table 1, Compound 3), 50 parts of polyvinyl chloride, and 50 parts of dioctyl phthalate was kneaded at 150 ° C. for 10 minutes, and the resulting dough was 160 ° C. It is crimped | bonded for 5 minutes between the metal plates heated by the process, and it is made into the sheet of thickness 0.5mm. The obtained sheet exhibits a bright fluorescent red color.

Example 5

0.01 part of thiophenoxythioindigo (Table 1, Compound 5) and 10 parts of polystyrene are made into a homogeneous mixture, which is then shrinked at 180 ° C. for several minutes and pressed onto a 5 mm thick disc.

The obtained disc exhibits a vivid fluorescent stone crimson.

Example 6

20 parts of melamine formaldehyde resin is added to 50 parts of sulfonamide resin melted at 120 ° C to make 170-180 ° C, and 1 part of 6-phenoxy-6'-methylthioindigo (Table 1, compound 7) is added and dissolved. .

When the solidified resin is pulverized after cooling, a fluorescent red-red pigment and a resin color base are obtained.

Claims (1)

General formula

(Wherein R represents a hydrogen atom or a lower alkyl group, R 'represents a hydrogen atom, a lower alkyl group, a lower alkoxy group or a halogen atom, R' 'represents a hydrogen atom or a methyl group, and X represents an oxygen atom or a sulfur atom) A novel asymmetric thioindigoide-based compound represented by ().